Stability and isomerization reactions of phenyl cation C6H5+ isomers

Shi, Dandan; Yang, Xue; Zhang, Xiaomei; Shan, Shimin; Xu, Haifeng; Yan, Bing

doi:10.1016/j.chemphys.2016.01.001

Cited by 3 publications

(4 citation statements)

References 26 publications

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“…Several chain-like C 6 H 5 + isomers exist, lying a couple of eVs above ground-state phenylium. 32 The structures investigated in Fig. 5 are amongst the lowest in energy.…”

Section: Fragmentation Chemistrymentioning

confidence: 96%

“…The 2.41 eV energy of ts3 compares very well with the value of 2.44 eV (56.2 kcal mol À1 ) obtained with CCSD(T) 22 while it is low compared to the 3.33 eV value obtained with QCISD(T). 32 Despite the uncertainties of the different methods, direct H-loss from phenylium is clearly energetically less favorable than isomerization.…”

Section: Fragmentation Chemistrymentioning

confidence: 99%

“…Such information is of importance as a structural rearrangement of phenylium would affect reaction and dissociation pathways that are of importance to the reaction networks in flames and the interstellar medium. Recently, Shi et al 32 theoretically explored the phenylium potential energy surface (PES), identifying 60 possible isomers in which they were able to connect 28 through transition states. A laboratory study on the photodissociation of the (neutral) phenyl radical found H-loss to occur upon irradiation at 248 nm and both H and [2C,2H]-loss at 193 nm.…”

Section: Introductionmentioning

confidence: 99%

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IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

Wiersma

Candian

Bakker

et al. 2021

Phys. Chem. Chem. Phys.

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“…Several chain-like C 6 H 5 + isomers exist, lying a couple of eVs above ground-state phenylium. 32 The structures investigated in Fig. 5 are amongst the lowest in energy.…”

Section: Fragmentation Chemistrymentioning

confidence: 96%

Section: Fragmentation Chemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

Wiersma

Candian

Bakker

et al. 2021

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

show abstract

“…The 2.41 eV energy of ts3 compares very well with the value of 2.44 eV (56.2 kcal/mol) obtained with CCSD(T) 22 while it is low compared to the 3.33 eV value obtained with QCISD(T). 32 Despite the uncertainties of the different methods, direct H-loss from phenylium is clearly energetically less favorable than isomerization.…”

Section: Fragmentation Chemistrymentioning

confidence: 99%

IR photofragmentation of the Phenyl Cation: Spectroscopy and Fragmentation Pathways

Wiersma,

Candian,

Bakker

et al. 2021

Preprint

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We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio (C 6 H + 5 ) and perdeutero (C 6 D + 5 ) forms, in the 260-1925 cm −1 (5.2-38 µm) spectral range, and investigate the observed photofragmentation. The spectral and fragmentation data were obtained using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy within a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR MS) located inside the cavity of the free electron laser FELICE (Free Electron Laser for Intra-Cavity Experiments). The 1 A 1 singlet nature of the phenylium ion is ascertained by comparison of the observed IR spectrum with DFT calculations, using both harmonic and anharmonic frequency calculations. To investigate the observed loss of predominantly [2C,nH] (n= 2 − 4) fragments, we explored the potential energy surface (PES) to unravel possible isomerization and fragmentation reaction pathways. The lowest energy pathways toward fragmentation include direct H elimination, and a combination of facile ring-opening mechanisms (≤ 2.4 eV), followed by elimination of H or CCH 2 . Energetically, all H-loss channels found are more easily accessible than CCH 2 -loss. Calculations of the vibrational density of states for the various intermediates show that at high internal energies, ring opening is the thermodynamically the most advantageaous, eliminating direct H-loss as a competing process. The observed loss of primarily [2C,2H] can be explained through entropy calculations that show favored loss of [2C,2H] at higher internal energies.

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Dissociative single and double photoionization of biphenyl (C12H10) by soft X-rays in planetary nebulae

Quitián-Lara

Fantuzzi

Oliveira

et al. 2020

Monthly Notices of the Royal Astronomical Society

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Biphenyl (C12H10), or phenylbenzene, is an important building block of polycyclic aromatic hydrocarbons (PAHs), whose infrared spectral features are present in a variety of galactic and extragalactic sources. In this work, we use synchrotron radiation coupled with time of flight spectrometry to study the photoionization and photodissociation processes of biphenyl upon its interaction with soft X-ray photons at energies around the inner-shell C1s resonance. These results are compared with our previous studies with benzene (C6H6) and naphthalene (C10H8), and discussed in the context of four planetary nebulae featuring PAH infrared emission: BD+30○3639, NGC 7027, NGC 5315 and NGC 40. We show that the mass spectrum of biphenyl before the C1s resonance energy is dominated by single photoionization processes leading to C6H5+, C6H4+· and C12H10+·, while after the resonance dissociation following multiple photoionization processes is dominant. The release of neutral C6H6 and C6H5· species accounts for one of the most relevant dissociation processes starting from the doubly-ionized biphenyl, indicating that heterolytic charge separation of the two phenyl rings is also achieved. By using quantum chemical calculations, we show that the biphenylic structure is a high-lying isomer of the singly- and doubly-ionized C12H10 species, whose minimum energy geometries are related to the acenaphthene molecule, composed of a C2-bridged naphthalene. Furthermore, we estimate the lifetime of biphenyl for 275 eV and 310 eV in photon-dominated regions of planetary nebulae. We discuss distinct processes that may enhance its lifetime and those of other small-sized PAHs in such astrophysical environments.

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Stability and isomerization reactions of phenyl cation C6H5+ isomers

Cited by 3 publications

References 26 publications

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways

IR photofragmentation of the Phenyl Cation: Spectroscopy and Fragmentation Pathways

Dissociative single and double photoionization of biphenyl (C12H10) by soft X-rays in planetary nebulae

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